KR20160019443A - Glare-free, microstructured, and specially coated film - Google Patents

Abstract

The present invention relates to a plastic film comprising an antiglare surface and a coating on said surface. The coating comprises at least 30 wt.% Of at least one thermoplastic polymer in the solids content of the coating composition; At least one UV-curable reactive diluent in an amount of at least 30% by weight of the solids content of the coating composition; At least one photoinitiator in a solids content of the coating composition of > = 0.1 to < = 10 parts by weight; And a coating composition comprising at least one organic solvent. The coating has a layer thickness in the range of ≥ 2 μm and ≤ 20 μm. The solids content of the coating composition is within the range of > 0 to < = 40 wt% as measured in relation to the total weight of the coating composition. Thus, an anti-glare film having excellent solvent resistance and excellent scratch resistance or pencil hardness is provided.

Description

GLUE-FREE, MICROSTRUCTURED, AND SPECIALLY COATED FILM < RTI ID = 0.0 >

The present invention relates to a coating composition for coating an anti-glare coated polymer film and an anti-glare polymer film. The invention further relates to an anti-glare anti-glare front plate for the display of anti-glare, product comprising coated films of the invention and displays, in particular for computer screens, televisions, display systems and cellular phones, , ≪ / RTI > electronic and automotive interior trims. The present invention also relates to a method of making an anti-glare coated film.

The anti-glare surface is understood to mean an optical surface with reduced specular reflection (Becker, ME and Neumeier, J., 70.4: Optical Characterization of Scattering Anti-Glare Layers, SID Symposium Digest of Technical Papers, 1038-1041). Typical applications of such surfaces are found in display technology, as well as in the fields of architecture, furniture, and the like. In this context, the anti-glare construction of the film is an object of particular interest due to its broad application.

For example, it is possible to use a surface-roughing surface (Huckaby, DKP & Caims, DR, 36.2, Quantifying "Sparkle" of Anti-Glare Surfaces, SID Symposium Digest of Technical Papers, 2009, 40, 511-513) 2010 ", by Liu, BT, Teng, YT, A novel method to control inner and outer haze of an anti-glare film by surface modification of light-scattering particles, Journal of Colloid and Interface Science, (Boerner, V., Abbott, S. Blaesi, B., Gombert, A., Hossfeld, W., 7.3, Blackwell Publishing Ltd., 2003, 34, 68-71) Various methods exist in the related art for imparting anti-glare properties to the surface of a film. Additional methods involve establishing a scatter function through phase separation at the surface layer (Stefan Walheim, Erik Schaeffer, Juergen Mlynek, Ullrich Steiner, Nanophase-Separated Polymer Films as High-Performance Antireflection Coatings, Science, 1999, 283 , 520-522).

A wide range of methods in the prior art for imparting anti-glare properties to the film surface involves embossing the microstructure onto the film surface. Transparent films especially used for this purpose are made, for example, from polycarbonates obtainable under the Makrofol® trade name, especially from the manufacturer Bayer Material Science AG. This type of film is produced, for example, by extrusion, in which the surface texturing of the film is produced by embossing with polycarbonate which has yet to be cooled incompletely using a particular roll. Films of this kind are available, for example, under the names Macrofol® 1-M and 1-4 from the manufacturer Bayer Material Science. The surface obtained in this way is thus anti-glare, but sensitive to many solvents, more ductile and susceptible to scratching.

A specific challenge is to achieve a high transparency of the film and a very substantial anti-glare surface at the same time. A further specific challenge for the artisan is not only to impart anti-glare properties to the surface of the film, but also to ensure that it is sufficiently scratch resistant, water resistant and solvent-resistant. In addition, in the field of display technology, readability or readability is a very important criterion for the usefulness of films in this field. It is difficult to realize the required profile, that is, to provide a transparent film having anti-glare and scratch resistant surfaces and a high level of water resistance and solvent resistance. There is therefore a particular need for a film that realizes this profile as required.

Surprisingly, it has been found that such a required profile can be achieved if the following are used: a polymer film having an anti-glare surface and a coating on the surface,

(a) at least one thermoplastic polymer in an amount of at least 30% by weight of the solids content of the coating composition;

(b) at least one UV-curable reactive diluent in an amount of at least 30% by weight of the solids content of the coating composition;

(c) at least one photoinitiator in a solids content of the coating composition of > = 0.1 to < = 10 parts by weight; And

(d) at least one organic solvent

≪ RTI ID = 0.0 > and / or < / RTI >

Wherein the coating has a layer thickness in the range of ≥ 2 μm and ≤ 20 μm and the solids content of the coating composition is in the range of ≥ 0 to ≤ 40 wt% based on the total weight of the coating composition.

The present invention thus provides:

An anti-glare polymeric film comprising a glare-proof surface and a polymeric film having a coating on the surface, the coating comprising

(a) at least one linear thermoplastic polymer in an amount of at least 30% by weight of the solids content of the coating composition;

(b) at least one UV-curable reactive diluent in an amount of at least 30% by weight of the solids content of the coating composition;

(c) at least one photoinitiator in a solids content of the coating composition of > = 0.1 to < = 10 parts by weight;

(d) at least one organic solvent

≪ RTI ID = 0.0 > and / or < / RTI >

Wherein the coating has a layer thickness in the range of ≥ 2 μm and ≤ 20 μm and the solids content of the coating composition is in the range of ≥ 0 to ≤ 40 wt% based on the total weight of the coating composition.

Preferably, the use of films of thermoplastic materials such as polycarbonates, polyacrylates or poly (meth) acrylates, polysulfones, polyesters, thermoplastic polyurethanes and polystyrenes, and copolymers and blends thereof (blends) It is possible. Suitable thermoplastic materials include, for example, polyacrylates, poly (meth) acrylates (e.g. PMMA; e.g. Plexiglas® from Roehm), cycloolefin copolymers (COC; For example, Topas® from the manufacturer Ticona; Zenoex® from the manufacturer Nippon Zeon or Apel® from Japan Synthetic Rubber, ), Polysulfone (Ultrason® from BASF or Udel® from manufacturer Solvay), polyesters such as PET or PEN, polycarbonate (PC), polycarbonate Polycarbonate / polyester blends such as PC / PET, polycarbonate / polycyclohexylmethanol cyclohexanedicarboxylate (PCCD; Xylecs® from the manufacturer GE), poly Carbonate / PBT and its Mixtures.

Particularly advantageous films have been found to be those made from polycarbonates or copolycarbonates, due to their transparency and their suitability for microstructuring for the purpose of anti-glare construction. An example of a polycarbonate film useful in a manner particularly advantageous to the present invention is a polycarbonate film supplied by Bayer Material Science Incorporated having a microstructured surface on one side and a glossy or smooth surface on another side . The film is available under the names 1-M and 1-4, one side (face 1) having a high gloss and the other face (face M or face 4) having a different microstructure. Cotton M or 4 is produced through the embossing action of rolls of different roughness in the course of the production of the film. These differ in the average depth of the embossed structure or the depth of illumination (Rz, DIN EN ISO 4287).

It is preferred to use polycarbonate or copolycarbonate. In a particularly preferred embodiment of the present invention, the polymer film comprises a polycarbonate film.

를 갖는다.Suitable polycarbonates for the preparation of the films of the present invention are all known polycarbonates. These are homopolycarbonates, copolycarbonates and thermoplastic polyester carbonates. Suitable polycarbonates preferably have a viscosity of from 18,000 to 40,000, preferably from 26,000 to 36,000, determined by measuring the relative solution viscosity in a mixture of phenol / o-dichlorobenzene in dichloromethane or equivalent weight, , In particular an average molecular weight of 28,000 to 35,000

.

The polycarbonate is preferably prepared by an interfacial method or a melt transesterification method, which has been described numerous times in the literature. With respect to the interfacial method, see, for example, H. Schnell, Chemistry and Physics of Polycarbonates, Polymer Reviews, vol. 9, Interscience Publishers, New York 1964 p. 33 ff., To Polymer Reviews, vol. 10, "Condensation Polymers by Interfacial and Solution Methods ", Paul W. Morgan, Interscience Publishers, New York 1965, ch. VIII, p. 325, to Drs. U. Grigo, K. Kircher and P. R. Mueller "Polycarbonates" [Polycarbonates] in Becker / Braun, Kunststoff-Handbuch [Polymer Handbook], volume 3/1, Polycarbonate, Polyacetal, Polyester, Celluloseester [Polycarbonates, Polyacetals, Polyesters , Cellulose Esters, Carl Hanser Publishers, Munich, Vienna, 1992, p. 118-145 and EP-A 0 517 044. The melt transesterification process is described, for example, in Encyclopedia of Polymer Science, vol. 10 (1969), Chemistry and Physics of Polycarbonates, Polymer Reviews, H. Schnell, vol. 9, John Wiley and Sons, Inc. (1964), and in patent specifications DE-B 10 31 512 and US-B 6 228 973.

Polycarbonates can be obtained from the reaction of bisphenol compounds with carbonic acid compounds, especially phosgene, or diphenyl carbonate or dimethyl carbonate in a melt transesterification process. Where homopolycarbonates based on bisphenol A and copolycarbonates based on monomeric bisphenol A and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane are particularly preferred, desirable. Further bisphenol compounds which can be used for polycarbonate synthesis are described in particular in WO-A-2008037364, EP-A-1 582 549, WO-A-2002/026862 and WO-A-2005/113639.

The polycarbonate may be linear or branched. It is also possible to use mixtures of branched and unbranched polycarbonates.

Suitable branching agents for polycarbonates are known in the literature and are described, for example, in patent specifications US-B 4 185 009, DE-A 25 00 092, DE-A 42 40 313, DE-A 19 943 642, US -B 5 367 044, and documents cited therein. In addition, when no branching agent is added to the course of polycarbonate preparation, the polycarbonate used may also be essentially branched. One example of a unique branch is referred to as the so-called Fries structure as disclosed for EP-A-1 506 249 for molten polycarbonate.

It is also possible to use chain termination in polycarbonate production. The chain termination used is preferably phenols such as phenol, alkylphenols such as cresol and 4-tert-butylphenol, chlorophenol, bromophenol, cumylphenol or mixtures thereof.

The optically at least partially anti-glare surface is understood to mean a surface on which the specular reflection is significantly reduced. The specular reflection is described by Snell's law when visible light striking a non-absorbing, smooth surface at a certain angle (incident angle) is reflected at the same angle (reflection angle). The two angles are formed perpendicular to the reflective surface (the theoretical normal to the surface). The anti-glare surface is achieved through proper roughening of the surface. When the light falls on a suitably roughened surface, the light is scattered in a diffused manner in different directions. In the context of the present invention, anti-glare surfaces are described, for example, in Becker, M.E. it is understood that the term refers to an optical interface in which the specular reflection is reduced as described in, for example, Neumer, J., and Neumeier, J., 70.4: Optical Characterization of Scattering Anti-Glare Layers, SID Symposium Digest of Technical Papers, SID, 2011, 42, 1038-1041 do. The anti-glare surface is preferably, for example, as described in Huckaby, D.K.P. &Quot; < / RTI > Caims, D.R., 36.2, Quantifying "Sparkle" of Anti-Glare Surfaces, SID Symposium Digest of Technical Papers, 2009, 40, 511-513. Preferably further or alternatively, for example, Liu, BT, Teng, YT, A novel method to control inner and outer haze of an anti-glare film by surface modification of light- Colloid and Interface Science, 2010, 350, 421-426, incorporated herein by reference. In addition or alternatively to the surface comprising the roughened surface or the particles, the anti-glare properties can be determined, for example, by the method of Boerner, V., Abbott, S, Blaesi, B., Gombert, A., Hossfeld May be imparted to at least one surface of a film according to the present invention by embossed micro- or nanostructured as described in W., 7.3, Blackwell Publishing Ltd., 2003, 34, 68-71. Additionally or alternatively, the anti-glare properties can be measured by, for example, the method of Stefan Walheim, Erik Schaeffer, Juergen Mlynek, Ullrich Steiner, Nanophase-Separated Polymer Films as High-Performance Antireflection Coatings, Science, 1999, 522] by at least one surface according to the present invention by phase separation at the surface. The contents of the cited references and therefore the disclosure thereof are incorporated herein by reference.

In general, the anti-glare configuration of the present invention more preferably comprises microstructuring the surface of the film to be coated according to the present invention, and in particular, microstructuring the coated surface of the film of the present invention. A suitable definition of microstructuring in the context of the present invention is advantageously the term "roughness" as used in DIN EN ISO 4287. According to DIN EN ISO 4287, the surface roughness is defined by the parameters Ra and Rz. Ra is the arithmetic mean of the absolute value of the profile deviation within the reference distance. Rz is the arithmetic mean of the largest individual illuminance from a plurality of adjacent individual measurement distances. Hereinafter, the parameter Rz, which can be determined in a reproducible manner in accordance with DIN EN ISO 4287, will be used to define the roughness of the film surface and thus the microstructuring.

The concept of the present invention is based on the roughness of the upper surface of the coating produced through the proposed roughness of the substrate to be coated. The anti-glare configuration of at least one side of the coated film of the present invention is such that at least one surface of the uncoated film is in the range of ≥ 500 and ≤ 4000 nm, preferably ≥ 700 and ≤ 3600 nm, more preferably ≥ 800 And an illuminance depth Rz in accordance with DIN EN ISO 4287 in the range of? 1500 nm, alternatively in the range of? 2000 and? 3800, preferably in the range of? 2500 and? 3600 nm .

For example, a film of the MacroPol 1-M (Bayer) or MacroPol 1-4 (Bayer) type having anti-glare properties on one side, for use in a particularly advantageous manner in the context of the present invention, Or an average illumination depth Rz in accordance with DIN EN ISO 4287 in the range of 2800 to 3500 nm.

In a particularly preferred embodiment of the invention, the microstructuring of the yet uncoated, anti-glare, at least one film surface is in the range ≥ 650 and ≤ 4000 nm, preferably ≥ 700 and ≤ 3600 nm, more preferably ≥ 800 and 1500 nm, alternatively ≥ 2000 and ≤ 3800, preferably ≥ 2500 and ≤ 3600 nm, according to DIN EN ISO 4287.

A specific challenge for a typical technician was to coat the surface of a film that has been imparted with anti-glare properties in a manner such that specific scratch resistance and solvent resistance are achieved first, but anti-glare properties are maintained. This object is achieved by a composition comprising at least 30% by weight of at least one thermoplastic polymer in the solids content of the coating composition; At least one UV-curable reactive diluent in an amount of at least 30% by weight of the solids content of the coating composition; At least one photoinitiator in a solids content of the coating composition of > = 0.1 to < = 10 parts by weight; Wherein the coating has a layer thickness in the range of ≥ 2 μm and ≤ 20 μm and the solids content of the coating composition is less than or equal to the total weight of the coating composition Is in the range of? 0 to? 40% by weight. The coating of the anti-glare surface of the film of the present invention is characterized by its excellent anti-blocking properties after application to the film and subsequent drying, as well as excellent solvent resistance and high scratch resistance after curing by actinic radiation. The anti-glare properties of the anti-glare surface of the film are retained when the coating of the invention has a layer thickness in the range of? 2 μm and? 20 μm.

The coating composition for application according to the invention is viscous; The viscosity increases very quickly when the solvent disappears in the course of drying after application. Thus, the dried coating is immediately fixed to the microstructured surface. No movement, slip or flow from the height to the depth of the microstructure is no longer possible. Even if the viscosity is high, the solids content of the coating composition is low, preferably ≥ 5 wt% to ≤ 40 wt%, more preferably ≥ 10 wt% to ≤ 30 wt%, and most preferably ≥ 15 wt% to ≤ 25 wt% By weight. With the rapid increase in viscosity in the course of drying, this enables a thin and relatively homogeneous coating of the height and depth of the microstructure of the antiglare structure of the film surface.

In general, the microstructured, anti-glare surface of the film becomes smoother and more transparent as a result of the application of the coating of the present invention. The roughness of the resulting coating decreases with the effective layer thickness of the coating so that in addition to the specific roughness value the film no longer has an anti-glare appearance, but instead has a glossy appearance.

According to the prior art, there is no sharp boundary between the anti-glare and the luminous appearance in terms of roughness value or in terms of other optical parameters. This is highly dependent on the manufacturing method and application. Two additional optical parameters that can possibly define this boundary are the reflection level Rs (60 degrees geometry) and haze.

An important parameter for the antiglare film is the haze obtained from the light scattering test method according to ASTM-D1003. In this method, scattering measured by transmission at a scattering angle of more than 2.5 [deg.] Was detected and normalized to the transmitted total intensity. The combination of the reflection level and the haze value generates a reasonable boundary for the anti-glare appearance of less than 70 +/- 10 GU (Rs) and greater than 6 +/- 2% (haze). In a further preferred embodiment of the present invention, the gloss value of the coating according to ASTM-D2457 at < RTI ID = 0.0 > 60 < / RTI >

The coated films of the present invention have anti-glare properties especially when they have a roughness Rz according to DIN EN ISO 4287 of at least 600 nm after curing of the coating and coating. In this context, it will be appreciated that the Rz value of the coated film surface can not be higher than the Rz of the corresponding uncoated anti-glare film surface. Proceeding from the case of a preferred film having an illumination depth Rz according to DIN EN ISO 4287 in the range of ≥ 650 and ≤ 4000 nm, preferably without coating, the coated film surface of the present invention is within this range, And also has a maximum roughness Rz within the preferred range mentioned. In a particularly preferred embodiment of the present invention, the coated film has an illuminance Rz according to DIN EN ISO 4287 of at least 600 nm.

Coated films of the present invention above 2 micrometer coating thickness have a distinct improvement in scratch resistance and solvent resistance as compared to uncoated films. Thus, the layer thickness of the coating composition of the film of the present invention is preferably at least 2 [mu] m, more preferably at least 4 [mu] m. In the case of a layer thickness of the coating of more than 20 [mu] m, by contrast, the roughness falls below a desirable value and the film surface no longer has an anti-glare appearance, but instead has a luminous appearance. Therefore, the layer thickness of the coating of the film of the present invention is preferably 20 [mu] m or less. In a preferred embodiment, the coating is in the range of ≥ 4 μm to ≤ 12 μm or a layer thickness in the range of ≥ 2 μm to ≤ 18 μm. Thus, the layer thicknesses of the coatings of the invention in particular in the range of ≥ 4 μm to ≤ 12 μm are particularly favorable for films with a roughness Rz in the range of 800 to 1300 nm, for example for anti-glare surfaces of the macropole 1-M type (Bayer) It is advantageous. To obtain anti-glare and simultaneously scratch-resistant and solvent-resistant surfaces, the layer thicknesses of the coatings of the invention in the range of ≥ 2 μm to ≤ 18 μm are determined by films having a roughness Rz in the range of 2800 to 3500 nm, Particularly beneficial especially on surfaces of type 1-4 (Bayer).

Additional optical parameters that can characterize the application-related anti-glare film are pre-spinning (DOI; test method: ASTM-D5767) and modulation transfer function (MTF). The latter is defined as the ratio of the contrast of the image and the object. A further option is the evaluation through the sparkle effect (Becker, ME & Neumeier, J .; 70.4: Optical Characterization of Scattering Anti-Glare Layers in SID Symposium Digest of Technical Papers, SID, 2011, 42, 1038-1041) Reference). According to the definition of the sparkle value (s = sigma / mu; i.e. the ratio of the variance (sigma) to the mean of the intensity distribution of the display with anti-glare film), a small value is the objective. For a DOI or MTF value, a large value (100%) is a target for generation.

In a further preferred embodiment of the present invention, the coated film has a DOI / MTF value of greater than 97%. A particularly preferred coated film according to the present invention thus has a gloss value according to ASTM-D2457 at 60 DEG of GU < 80 with a Rz according to DIN EN ISO 4287 of at least 600 nm, preferably greater than 97% DOI / And at least one coated surface in combination with the MTF value.

The coating of at least one anti-glare surface of the film of the present invention

(a) at least one thermoplastic polymer in an amount of at least 30% by weight of the solids content of the coating composition;

(b) at least one UV-curable reactive diluent in an amount of at least 30% by weight of the solids content of the coating composition;

(c) at least one photoinitiator in a solids content of the coating composition of > = 0.1 to < = 10 parts by weight; And

(d) at least one organic solvent

Wherein the solids content of the coating composition is in the range of ≥ 0 to ≤ 40 wt%, preferably ≥ 5 wt% to ≤ 40 wt%, more preferably ≥ 10 wt%, based on the total weight of the coating composition, To < = 30 wt%, and most preferably > = 15 wt% to 25 wt%. The coating composition thus forms a further part of the subject matter of the present invention.

The Vicat softening temperature VET (ISO 306) of the at least one thermoplastic polymer in the coating according to the invention is in the preferred embodiment of the invention at least about 90 캜, preferably at least 95 캜, more preferably at least 100 캜 to be.

The surface of the coating has been found to be particularly scratch resistant and content, especially when at least one thermoplastic polymer has an average molar mass Mw of at least 100,000 g / mol. In a preferred embodiment of the present invention, the thermoplastic polymer has an average molar mass Mw of at least 100,000 g / mol, preferably at least 150,000 g / mol, more preferably at least 200,000 g / mol.

In the context of the present invention, the thermoplastic polymers are, in particular, polymethylmethacrylate (PMMA), various types of polyesters (e.g. PET, PEN, PBTP and UP), other polymers such as hard PVC, CP), polystyrene (PS) and copolymers (SAN, SB and MBS), polyacrylonitrile (PAN), ABS polymers, acrylonitrile-methyl methacrylate (AMMA), acrylonitrile- (PP), polyamide (PA), polycarbonate (PC), or polyethersulfone (PE)), polyurethane (PES). The above abbreviations of polymers and copolymers are defined in DIN 7728T1.

Polymethyl methacrylate is particularly advantageous and is therefore particularly preferred.

Polymethyl methacrylate (PMMA) is understood to mean a methyl methacrylate-based copolymer having a polymethyl methacrylate homopolymer and a methyl methacrylate content of greater than 70% by weight. Such polymethylmethacrylates are commercially available, for example, under the trade names Degalan, Degacryl, Plexiglass, Acrylite (Evonik), Aldoglass Under the trade name of Algal®, Altuglas, Oroglas (manufacturer: Arkema), Elvacite®, Colacryl®, Lucite® (manufacturer: Lucite) Such as, for example, acrylic resins such as Acrylglas, Conacryl, Deglas, Diakon, Friacryl, Hesaglas, Limacryl, PerClax, (Vitroflex).

In a further advantageous embodiment, copolymers of PMMA homopolymer and / or 70% to 99.5% by weight of methyl methacrylate and 0.5% to 30% by weight of methyl acrylate are preferred. Copolymers of PMMA homopolymers and copolymers of 90% by weight to 99.5% by weight methyl methacrylate and 0.5% by weight to 30% by weight methyl acrylate are particularly preferred. These preferred PMMA homopolymers and / or Vicat softening temperatures VET (ISO 306) may be at least about 90 캜, preferably ≥ 100 캜 to ≤ 115 캜.

Particularly preferred are PMMA homopolymers and copolymers having a molecular weight Mw of at least 100,000 g / mol, more preferably at least 150,000 g / mol, very particularly at least 200,000 g / mol.

The molecular weight Mw can be determined, for example, by gel permeation chromatography or by a scattered light method (see, for example, HF Mark et al., Encyclopedia of Polymer Science and Engineering, 1 ff., J. Wiley, 1989).

The polymer is an integral part of the coating composition of the present invention and the coating of the present invention. The proportion of thermoplastic polymer in the solids content of the coating composition is at least 30% by weight. Particularly preferably 40% by weight, particularly preferably 45% by weight.

Reactive diluents that can preferably be used as component (b) of the coating composition of the present invention are bifunctional, trifunctional, tetrafunctional, bifunctional or hexafunctional acrylic and / or methacrylic monomers. Especially preferred is an ester functional group, particularly an acrylic ester functional group. Suitable polyfunctional acrylic acid or methacrylic acid esters are prepared from aliphatic polyhydroxyl compounds having at least two, preferably at least three, more preferably at least four hydroxyl groups, and preferably from 2 to 12 carbon atoms .

Examples of such aliphatic polyhydroxyl compounds include ethylene glycol, propylene glycol, butane-1,4-diol, hexane-1,6-diol, diethylene glycol, triethylene glycol, glycerol, trimethylolpropane, pentaerythritol, di Pentaerythritol, tetramethylol ethane and sorbitan. Examples of esters which are preferably suitable according to the invention as reactive diluents are glycol diacrylate and dimethacrylate, butanediol diacrylate or dimethacrylate, butylene glycol diacrylate or dimethacrylate, diethylene glycol Diacrylate or dimethacrylate, divinylbenzene, trimethylolpropane triacrylate or trimethacrylate, glyceryl triacrylate or trimethacrylate, pentaerythrityl tetraacrylate or tetramethacrylate, di (DPHA), butane-1,2,3,4-tetraol tetraacrylate or tetramethacrylate, tetramethylol ethane tetraacrylate or tetramethacrylate, 2, 3-tetraethylene tetraacrylate, 2-dihydroxypropane-1,3-diol tetraacrylate or tetramethacrylate Agent, di-urethane dimethacrylate (UDMA), sorbitan tetra-, penta-or hexa acrylate or the corresponding methacrylates. It is also possible to further use mixtures of crosslinking monomers having 2 to 4 or more ethylenically unsaturated, free-radically polymerizable groups.

In addition, according to the present invention it is possible to use alkoxylated di-, tri-, tetra-, penta- and hexaacrylates or -methacrylates as reactive diluents or as component b) of the coating compositions of the invention. Examples of alkoxylated diacrylates or methacrylates are alkoxylated, preferably ethoxylated, methanediol diacrylate, methanediol dimethacrylate, glyceryl diacrylate, glyceryl dimethacrylate, neopentyl Diethylene glycol diacrylate, glycol diacrylate, neopentyl glycol dimethacrylate, 2-butyl-2-ethylpropane-1,3-diol diacrylate, Trimethylolpropane diacrylate or trimethylolpropane dimethacrylate.

Examples of alkoxylated triacrylates or methacrylates are alkoxylated, preferably ethoxylated, pentaerythrityl triacrylate, pentaerythrityl trimethacrylate, glyceryl triacrylate, glyceryl trimethacrylate Butane-1,2,4-triol triacrylate, butane-1,2,4-triol trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tricyclodecane di Methanol diacrylate, tricyclodecane dimethanol dimethacrylate, ditrimethylol propane tetraacrylate or ditrimethylol propane tetramethacrylate.

Examples of alkoxylated tetra-, penta- or hexaacrylates are alkoxylated, preferably ethoxylated, pentaerythrityl tetraacrylate, dipentaerythrityl tetraacrylate, dipentaerythrityl pentaacrylate, di Pentaerythrityl tetra methacrylate, dipentaerythrityl tetramethacrylate, dipentaerythrityl penta methacrylate, or dipentaerythrityl hexa methacrylate.

In component b), an alkoxylated diacrylate or methacrylate, triacrylate or methacrylate, tetraacrylate or methacrylate, pentaacrylate or methacrylate and / or alkoxylated hexaacrylate or In methacrylates, all acrylate groups or methacrylate groups in a respective monomer or only a portion of acrylate or methacrylate groups may be bonded to the corresponding radicals through an alkylene oxide group. It is also possible to use any desired mixture of such fully or partially alkoxylated di-, tri-, tetra-, penta- or hexaacrylates or -methacrylates. In this case, it is also possible for the acrylate or methacrylate group (s) to be bonded to the aliphatic, cycloaliphatic or aromatic radical of the monomer via a plurality of successive alkylene oxide groups, preferably ethylene oxide groups. The average number of alkylene oxide or ethylene oxide groups in the monomers is referred to by the degree of alkoxylation or ethoxylation. The level of alkoxylation or ethoxylation is preferably from 2 to 25, with an alkoxylation level or ethoxylation level of from 2 to 15 being particularly preferred, with from 3 to 9 being most preferred.

Likewise, according to the present invention, the reactive diluent or component b) of the coating composition of the present invention may be an oligomer belonging to the class of aliphatic urethane acrylates or polyester acrylates or polyacryloyl acrylates. Its use as a paint binder is well known and is described in Chemistry & Technology of UV & EB Formulation for Coatings, Inks & Paints, vol. Polyester Acrylates), which is commercially available in the context of the present invention, is described in U.S. Patent No. 5,301,991, SITA Technology, London (PKT Oldring (ed.) On p. 73-123 (Urethane Acrylates) Illustrative examples include aliphatic urethane acrylates such as Ebecryl® 4858, Ebecryl® 284, Ebecryl® 265, Ebecryl® 264, Ebecryl® 8465, Ebecryl® 8402 (each manufactured by Cytec Surface Craynor® 925 from Cray Valley, Viaktin® 6160 from Vianova Resin, and Desmorux® from Bayer Material Science, Inc., all of which are commercially available from Bayer MaterialScience AG, Such as Desmolux VP LS 2265, Photomer 6891 from Cognis or other aliphatic urethane acrylates dissolved in a reactive diluent such as Laromer® 8987 from BASF AG (Hexanediol 70% of diacrylate), Desmorux U 680 H (80% in hexanediol diacrylate), Bayer MaterialScience AG, Craynor® 945B85 (85% in hexanediol diacrylate), Ebecryl 294 / 25HD (75% in hexanediol diacrylate), Ebecryl 8405 (80% in hexanediol diacrylate), Ebecryl 4820 (65% in hexanediol diacrylate) (each by Cytech Surface Specialty (80% in hexanediol diacrylate) (each from Cray Valley), or other polyester acrylates from Cytech Surface Specialty, such as Ebecryl 810, 830, or polyacryloyl 1 acrylate such as Ebecryl®, 740, 745, 767 or 1200.

In a further preferred embodiment, the reactive diluent (b) is selected from the group consisting of alkoxylated diacrylates and / or dimethacrylates, alkoxylated triacrylates and / or trimethacrylates, alkoxylated tetraacrylates and / or tetramethacrylates Alkoxylated and / or pentamethacrylates, alkoxylated hexaacrylates and / or hexamethacrylates, aliphatic urethane acrylates, polyester acrylates, polyacryloyl acrylates, and mixtures thereof .

Also according to the present invention there is a mixture of such a crosslinking multifunctional monomer and a monofunctional monomer such as methyl methacrylate. The proportion of the multifunctional monomer in such a mixture should not be less than 20% by weight.

Component (b) is an integral part of the coating composition of the present invention and the coating of the present invention. The total proportion of component (b) in the solids content of the coating composition is at least 30% by weight. At least 40% by weight is particularly preferred, and at least 45% by weight is very particularly preferred.

The content of ethylenically unsaturated groups has a significant influence on the achievable durability characteristics of the radiation-cured coating. Thus, the coating composition of the present invention is preferably at least 3.0 moles per kg of solids content of the coating composition, more preferably at least 3.5 moles per kg of solids content of coating composition, most preferably at least 4.0 moles of ethylenically unsaturated Lt; / RTI > content. This content of ethylenically unsaturated groups is also well known to those of ordinary skill in the art by the term "double bond density ".

The photoinitiators of the present invention can be prepared by reacting a compound of formula (I), a commercially available compound, such as, for example,? -Hydroxy ketone, benzophenone,?,? - diethoxyacetophenone, 4,4-diethylaminobenzophenone, Propyl ketone, 1-hydroxycyclohexyl phenyl ketone, isoamyl p-dimethyl aminobenzoate, methyl 4-dimethyl aminobenzoate, methyl benzoyl benzoate, benzoin benzoate, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-hydroxy-2-methyl-1-phenylpropan- Trimethylbenzoyldiphenylphosphine oxide, bisacylphosphine oxide, and the like, and the photoinitiator may be used singly or in combination with two or more of the polymerization initiators and They can be used in combination or in combination with one kind.

UV photoinitiators used include, for example, IRGACURE ® products from BASF, such as Irgacure ® 184, Irgacure ® 500, Irgacure ® 1173, Irgacure ® 2959, Irgacure® 745, Irgacure® 651, Irgacure® 369, Irgacure® 907, Irgacure® 1000, Irgacure® 1300, Irgacure® 819, Irgacure® 819DW, Irga Cure® 2022, Irgacure® 2100, Irgacure® 784, Irgacure® 250; DAROCUR ® products from BASF, for example DAROCURE® MBF, DAROCURE® 1173, DAROCURE® TPO and DAROCURE® 4265, are also used. Among other materials, additional UV photoinitiators such as Esacure One (manufacturer: Lamberti) are used.

The photoinitiator is present in a solids content of the coating composition of the present invention of > = 0.1 to < = 10 parts by weight.

The coating composition may additionally contain, in addition to the components a) to c), 100 parts by weight of the solids content of one or more organic solvents. Such organic solvents may be, for example, aromatic solvents such as xylene or toluene, ketones such as acetone, 2-butanone, methyl isobutyl ketone, diacetone alcohol, alcohols such as methanol, ethanol, i Propanol, butanol, 1-methoxy-2-propanol, ethers such as 1,4-dioxane, ethylene glycol n-propyl ether or esters such as ethyl acetate, butyl acetate, 1-methoxy- Propyl acetate, 2-propyl acetate, or a mixture comprising these solvents.

Ethanol, i-propanol, butanol, ethyl acetate, butyl acetate, 1-methoxy-2-propanol, diacetone alcohol, xylene or toluene and mixtures thereof are preferred. Particularly preferred are i-propanol, butanol, ethyl acetate, butyl acetate, 1-methoxy-2-propanol, diacetone alcohol and mixtures thereof. Methoxy-2-propanol and diacetone alcohol are very particularly preferred. 1-methoxy-2-propanol is particularly emphasized and is therefore preferred, since it is advantageously wholly neutral in its behavior with respect to the polycarbonate and does not affect the average roughness Rz of the anti-glare surface.

The coating composition of the present invention preferably comprises from 0 to 900 parts by weight, more preferably from 100 to 850 parts by weight, most preferably from 200 to 800 parts by weight of at least 100 parts by weight of at least one compound selected from the group consisting of It contains one kind of organic solvent.

In a very particularly preferred embodiment of the present invention, the coated anti-glare film of the present invention has a microstructured surface with a Rz in the range of ≥ 800 to ≤1300 nm or ≥ 2800 to ≤ 3500 nm, and a microstructure of at least 100,000 g / mol By weight of at least one linear PMMA copolymer having an average molar mass of from 45 to 50% by weight; 45 to 50% by weight of at least one reactive diluent, especially dipentaerythritol penta / hexaacrylate; 0.1 to 10 parts by weight of at least one photoinitiator; And a coating obtainable by coating with a coating composition comprising 1-methoxy-2-propanol as an organic solvent, wherein the coating composition is present in an amount of from 4.5 to < RTI ID = 0.0 > Having an ethylenic unsaturation content of 5.5 mol and a solids content in the range of from 15 to 25% by weight, the coating having a roughness Rz in the range of ≥ 600 and ≤ 1300 nm and having a coated anti-glare surface according to ASTM-D2457 at 60 ° The gloss value GU of 80 or less.

The coating composition according to the present invention may further optionally contain, in addition to 100 parts by weight of components a) to c), one or more additional coating additives. Such coating additives may be selected from the group including, for example, stabilizers, smoothing agents, surface additives, pigments, dyes, inorganic nanoparticles, adhesion promoters, UV absorbers, IR absorbers, preferably stabilizers, And inorganic nanoparticles. The coating composition of the present invention comprises, in a preferred embodiment, from 100 parts by weight of components a) to c), ≥ 0 to ≤ 35 parts by weight, more preferably ≥ 0 to ≤ 30 parts by weight, most preferably ≥ 0.1 To 20 parts by weight of at least one further coating additive. Preferably, the total proportion of all coating additives present in the coating material composition is ≥ 0 to ≤ 35 parts by weight, more preferably ≥ 0 to ≤ 30 parts by weight, and most preferably ≥ 0.1 to ≤ 20 parts by weight.

The coating composition may include inorganic nanoparticles to increase mechanical durability, e.g., scratch resistance and / or pencil hardness.

Useful nanoparticles include inorganic oxides, mixed oxides, hydroxides, sulfates, carbonates, carbides, borides and nitrides of elements of families II to IV and / or elements of transition groups I to VIII of the periodic table containing lanthanides . Preferred nanoparticles are silicon oxide, aluminum oxide, cerium oxide, zirconium oxide, niobium oxide, zinc oxide or titanium oxide nanoparticles, with silicon oxide nanoparticles being particularly preferred.

The particles preferably used have an average particle size (measured by dynamic light scattering in dispersion, determined as Z-average) of less than 200 nm, preferably 5 to 100 nm, more preferably 5 to 50 nm . Preferably at least 75%, more preferably at least 90%, even more preferably at least 95% of all nanoparticles used have a size as defined above.

The coating composition may be prepared by first dissolving the polymer in the solvent at room temperature or at elevated temperature, then adding the other necessary and optional ingredients to the solution cooled to room temperature, combining them in the absence of solvent (s) By mixing them together in the presence of solvent (s), for example by adding them to the solvent (s) and mixing them together by stirring. Preferably, the photoinitiator is first dissolved in the solvent (s), and then additional ingredients are added. Followed by purification optionally by filtration, preferably by microfiltration.

The present invention, therefore,

(i) providing a film having at least one anti-glare surface of the film;

(ii) film against the surface of the anti-glare surface

(a) at least one thermoplastic polymer in an amount of at least 30% by weight of the solids content of the coating composition;

(b) at least one UV-curable reactive diluent in an amount of at least 30% by weight of the solids content of the coating composition;

(c) at least one photoinitiator in a solids content of the coating composition of > = 0.1 to < = 10 parts by weight; And

(d) at least one organic solvent

Wherein the coating has a layer thickness in the range of ≥ 2 μm and ≤ 20 μm and the solids content of the coating composition is ≥ 0 to ≤ 40 wt% based on the total weight of the coating composition, A step within the range;

(iii) drying the coating;

(iv) optionally cutting the film to a specified size and / or delaminating, printing and / or thermally or mechanically molding the film; And

(v) irradiating the coating with actinic radiation to cure the coating

≪ RTI ID = 0.0 > a < / RTI > coated film.

The film may be coated by a standard method for coating films using a fluid coating composition, for example by knife-coating, spraying, injection, flow-coating, dipping, rolling or spin-coating using a coating composition . The flow-coating method can be carried out either manually with a hose or a suitable coating head, or automatically and continuously by means of a flow-coating robot and optionally a slot die. Application of the coating composition by roll-to-roll transfer is preferred. In this case, the surface of the film to be coated may be pretreated by cleaning or activation.

Drying follows application of the coating composition to a substrate, preferably a film. For this purpose, more particularly, for example in a convection oven or in an oven by a nozzle dryer, and also moving and optionally also dry air, and heat radiation such as IR and / or NIR are used. It is also possible to use a microwave. It is possible and advantageous to combine a number of these drying methods. The drying of the coating in step (ii) preferably comprises a flash-off at room temperature and / or elevated temperature, such as preferably 20-200 ° C, more preferably 40-120 ° C. After the coating is dried, it is resistant to blocking, so that the coated film can be laminated, printed and / or thermally formed. Molding is particularly preferred in this context because it is possible here to define a mold for a film insert molding method for the manufacture of three-dimensional plastic parts.

Advantageously, the conditions for drying are chosen such that the elevated temperature and / or heat radiation does not trigger any polymerization (crosslinking) of the acrylate or methacrylate groups, which may impair the moldability. Also, the maximum temperature achieved should suitably be chosen at a sufficiently low level to ensure that the film is not deformed in an uncontrolled manner.

After the drying / curing step, the coated film may optionally be wound after lamination to a protective film against the coating. The film may be wound without a coating adhered to the back surface of the substrate film or the laminated film. However, it is also possible to cut the coated film to a certain size and to send the cut sections individually or as a stack to further processing.

Curing with actinic radiation is understood to mean free-radical polymerization of ethylenically unsaturated carbon-carbon double bonds with initiator radicals released from the photoinitiators described above, for example, by irradiation with actinic radiation.

Radioactive curing is preferably carried out by the action of high-energy radiation, i.e. UV radiation or daylight, for example light of a wavelength of ≥ 200 nm to ≤ 750 nm, or by the action of high-energy electrons (electron beams, for example ≥ 90 keV ≪ = 300 keV). The source of radiation used for light or UV light is, for example, a medium pressure or high pressure mercury vapor lamp, where the mercury vapor can be modified by doping with other elements such as gallium or rail. A laser, a pulse lamp (also known as a UV flashlight emitter), a halogen lamp or an excimer emitter can be used as well. The emitter may be set at a fixed position such that the material to be irradiated is moved past the radiation source by a mechanical device, or the emitter may be mobile and the material to be irradiated does not change position during the course of curing. Typically a sufficient dose of radiation for crosslinking in the case of UV curing is in the range of? 80 mJ / cm ² to? 5000 mJ / cm ² .

In a preferred embodiment, actinic radiation is thus light within the UV light range.

The irradiation may optionally be carried out under the exclusion of oxygen, for example under an inert gas atmosphere or a reduced-oxygen atmosphere. Suitable inert gases are preferably nitrogen, carbon dioxide, noble gases or combustion gases. The irradiation can also be carried out by covering the coating with radiation and a transparent medium. Examples thereof are polymer films, glass or liquids such as water.

Depending on the dose of radiation and the curing conditions, the type and concentration of any initiator used may be varied or optimized in a manner known to the ordinarily skilled artisan or by an exploratory preliminary test. In order to cure the molded film, it is particularly advantageous to carry out the curing with various emitters, and its arrangement should be chosen to provide a substantially optimal dose and intensity for curing at all points for the coating. More particularly, un-illuminated areas (shadow areas) should be avoided.

Further, depending on the film to be used, it may be advantageous to select the irradiation condition so that the thermal stress on the film is not excessively large. In particular, thin films and films made from materials having a low glass transition temperature may have a tendency towards uncontrolled deformation, especially when the temperature is exceeded as a result of irradiation. In these cases, it is advantageous to allow a minimum level of infrared radiation to act on the substrate by a suitable filter or an appropriately designed emitter. Also, a reduction in the corresponding dose of radiation can interfere with uncontrolled deformation. However, it should be noted that specific doses and intensities are required for the maximum polymerization in the investigation. In these cases it is particularly advantageous to carry out the curing under inert or reduced-oxygen conditions, because the dose required for curing decreases when the oxygen content is reduced in the atmosphere above the coating.

It is particularly preferred to use mercury emitters in stationary installations for curing. In this case, the photoinitiator is used at a concentration of > = 0.1 wt% to > 10 wt%, more preferably > 0.2 wt% to 3.0 wt%, based on the solids content of the coating. The coating is preferably cured using a dose of ≥ 80 mJ / cm ² to ≤ 5000 mJ / cm ^2.

The resulting cured, coated, optionally formed films are shown by coupling with solvents, very good resistance to dyeing fluids originating from the home, and high hardness, good scratch resistance and abrasion resistance with high optical transparency and anti-glare properties .

The film or other sheet is preferably used in a thickness of ≥ 10 μm to ≤ 1500 μm, more preferably ≥ 50 μm to ≤ 1000 μm, particularly preferably ≥ 200 μm to ≤ 400 μm. In addition, the film material may comprise additives and / or processing aids for making films, such as stabilizers, light stabilizers, plasticizers, fillers such as fibers and dyes.

In one embodiment, the film is a polycarbonate film having a thickness of? 10 μm to? 1500 μm. Which likewise comprises a polycarbonate film having the abovementioned additives and / or processing aids. The thickness of the film may also be ≥ 50 μm to ≤ 1000 μm or ≥ 200 μm to ≤ 400 μm.

The film may be coated on one or both sides, and a single-sided coating is preferred. In the case of a single-sided coating, the thermoformable adhesive layer may optionally be applied to the backside of the film, i.e. the surface to which the coating composition is not applied. For this purpose, according to the procedure, preferably a hot melt adhesive or a radiation-curable adhesive is suitable. It is also possible to apply a thermally moldable protective film to the surface of the adhesive layer as well. It is also possible to provide films with a backing material, such as a fabric, on the back, but they must be moldable to the desired extent.

Due to the outstanding properties mentioned, the coated films of the present invention are suitable for use in products in many industries, especially those requiring anti-glare or at least matte surfaces with high mechanical and chemical stability. The present invention thus further provides an article comprising at least one transparent coated polymer film according to the invention, said article being characterized in that it comprises an architectural glazing element, for example, more particularly, for example, , A covering plate glass, and a front plate glass for a display. Equally desirable products are matte plastic parts for electric, electronic and automotive trim. In a preferred embodiment of the present invention, the display is a computer screen, a television, a display system and a display of a mobile phone. In a further preferred embodiment of the invention, the product is an absence of a car trim, for example a dashboard.

The present invention further provides the use of the anti-glare coated polymeric film of the present invention as a highly transparent anti-glare frontal sheet glass for a display. In a preferred embodiment of the use of the invention of the coated film of the present invention, the display is a computer screen, a television, a display system and a display of a cellular phone.

Example:

Assessment Methods

The layer thickness of the coating was measured by observing the cutting-edge in an Axioplan optical microscope made by Zeiss. Method - Reflected light, bright field, magnification 500x.

Evaluation of Pencil Hardness

Pencil hardness was measured similarly to ASTM D 3363 under a load of 500 g using an Elcometer 3086 Scratch boy (Elcometer Instruments GmbH, Allen, Germany) unless otherwise noted .

Evaluation of steel wool scratching

Steel wool scratching was determined by adhering pieces of No. 00 steel wool (Oskar Weil GmbH Rakso, Lahr, Germany) onto a flat end of a 500 g peter hammer, and the area of the hammer was 2.5 cm x 2.5 cm , I.e., approximately 6.25 cm < ^{2 &} gt ;. Without applying additional pressure, the hammer was placed on the surface to be tested to achieve a limiting load of about 560 g. The hammer was then moved back and forth ten times in the twin stroke. Subsequently, the stressed surface was cleaned with a soft fabric to remove fabric residues and coated particles. Scratching was characterized by haze and gloss values and was measured using a Micro HAZE Plus (20 ° gloss and haze; Byk-Gardner GmbH, Germany Gertr. Direction. Measurements were made before and after scratching. The difference values for gloss and haze before and after the stress were recorded as delta gloss and DELTA haze.

Evaluation of content mashing

The solvent resistance of coatings was typically tested using technology-grade quality isopropanol, xylene, 1-methoxy-2-propyl acetate, ethyl acetate, acetone. The solvent was applied to the coating using a wet swab and protected from evaporation by covering. Unless otherwise noted, a contact time of about 60 minutes at about 23 占 폚 was observed. After the end of the contact time, the swab was removed and the test surface wiped clean with a soft cloth. The inspection was performed visually immediately after gentle scratching with the fingernail.

Differences in the following levels:

0 = unchanged; Visible change; Can not be damaged by scratching.

1 = Visibly more or less swollen, but not damaged by scratching.

ㆍ 2 = Apparent visible change, barely damaged by scratching.

ㆍ 3 = Notable change, surface destruction after hard nail pressure.

4 = significant change, scratching against the substrate after hard nail pressure.

ㆍ 5 = destroyed; When wiping out the chemical, the coating is already broken; The test substance can not be removed (absorbed into the surface).

In this evaluation, the test is typically passed with a rating of 0 and 1. A rating of> 1 indicates "failure".

Evaluation of optical properties

The transmission and haze were determined according to ASTM-D2457 using BYK Haze Gard (from Vick, Germany). The gloss was measured according to DIN 67530 using BYK micro Tri Gloss (from Vick, Germany). The illuminance values Ra and Rz were determined according to DIN ISO 4287 using a Dektak 150 Profiler from Veeco Instruments (USA). For determination of additional optical parameters of the sparkle, SMS 1000 (Sparkle Measurement System) from DOI / MTF and Rs, DM & S (Germany) was used.

Example 1: Preparation of the coating composition of the present invention

In a 15 l tank, first, degacril MW 730 (a copolymer based on PMMA, M _w = ¹⁰⁶ ; ebonic) was dissolved in 1-methoxy-2-propanol at 100 ° C (internal temperature) as follows 4500 g of 1-methoxy-2-propanol was charged first, and 1100 g of decagel MW 730 was introduced with stirring. Thereafter, they were rinsed with 2500 g of 1-methoxy-2-propanol. Dissolving takes about 4 hours. The results were homogeneous, clear, colorless, viscous. After the dissolution operation, the mixture was cooled to room temperature. 1100 g of dipentaerythritol penta / hexaacrylate (DPHA, manufacturer: Cytec) were individually diluted with 2500 g of 1-methoxy-2-propanol. At room temperature, this solution was added to the apparatus and mixed for 2 hours. 44.0 g of IRGACURE 1000 (BASF), 22.0 g of DAROCURE 4265 (BASF) and 5.5 g of BIG 333 (manufacturer: VIC) were individually diluted with 400 g of 1-methoxy-2-propanol. When the solution became homogeneous, it was added to the apparatus and mixed thoroughly. The mixture was stirred under exclusion of light for about 6 hours. Yield: 11,363 g. The coating composition obtained in this way had a solids content of 17% and a viscosity (23 DEG C) of 9000 mPas. In the solids content of the coating composition, the proportion of the higher polymer, and likewise the proportion of reactive diluent, was 48.4 wt.% Each. The content of ethylenically unsaturated groups per kg of solids content of the coating composition was about 5.2 mol.

Example 2 Coating of Film

The coating composition obtained in Example 1 was applied by means of a slot coater to a structured side of a backing film such as a macro-pole DE 1-M or a macro-pole DE 1-4 (Bayer MaterialScience AG, Leverkusen, Germany).

Typical application conditions are as follows:

ㆍ Web speed 1.3 to 2.0 m / min

Applied wet coating material 20-150 μm

Air circulation dryer 90-110 ° C, preferably in the region of the TG of the polymer to be dried.

ㆍ Retention time in the dryer 3.5-5 minutes.

Roll to roll was performed on the coating, which means that the polycarbonate film was not rolled in the coating system. The film was run through one of the above-mentioned application units and contacted with the coating solution. Thereafter, the film having the wet coating was allowed to pass through the dryer.

After leaving the dryer, it is now applied to UV curing to provide a laminated film to protect the dried coating from damage and scratching. Thereafter, the film was rewound. This work was carried out continuously in a roll-to-roll coating system designed for this purpose.

Example 3: Coated film based on substrate macroport DE 1-M

A variety of macropole DE 1-M films with a thickness of 250 [mu] m were coated using the coating composition from Example 1 in the process according to Example 2. Different film thicknesses of the coatings were prepared. In this way, the following film products were obtained (each layer thickness is mentioned in parentheses): B-3-1 (5 μm), B-3-2 (7 μm), B-3-3 μm), B-3-4 (15 μm), and B-3-5 (19 μm).

Example 4: Coated film based on substrate Macrofol DE 1-4

A variety of macropole DE 1-4 films with a thickness of 250 μm were coated using the coating composition from Example 1 in the process according to Example 2. Different film thicknesses of the coatings were prepared. In this way, the following film products were obtained (each layer thickness is mentioned in parentheses): B-4-1 (2 μm), B-4-2 (4 μm), B-4-3 B-4-7 (11 μm), B-4-5 (15 μm) B-4-6 (21 μm), B-4-7 (28 μm), B-4-8 ).

Example 5: Pencil hardness, steel wool scratching, solvent resistance

The coated films obtained in Examples 4 and 5 were tested for pencil hardness, steel wool scratching and solvent resistance by the specified test method. The results are summarized in Table 1.

B-3 is a coated film from Example 3; B-4 is a coated film from Example 4; 1-1 substrate is a macroporous DE < RTI ID = 0.0 > 1-1 film (Bayer), which has two smooth surfaces and functions as a comparative example)

Table 1 shows that the coatings of the present invention ensure good coverage of the structured polycarbonate surface, even at thin layers starting from all the thicknesses selected, even at 2 μm. All coated samples are solvent-resistant. In contrast, uncoated polycarbonates are highly susceptible to 1-methoxy-2-propyl acetate, xylene, ethyl acetate and acetone.

The same applies to the scratch resistance in the steel wool test. Here again it can be seen that the coating for all samples ensures protection of the polycarbonate surface regardless of the thickness of the coating material. The pencil hardness of the coated surface increases by 4-5 units compared to the uncoated film.

Example 6: Optical properties

Coated films B-3 and B-4 obtained in Examples 3 and 4, with commercially available anti-glare films, were evaluated in terms of optical properties. This involved determining the transmission (normal incidence of light), haze, gloss and roughness by the above-mentioned method. For this comparison, two different AG films from MSK (Japan) were examined. Thus, these commercial AG films exhibit a haze value of 6 to 11%; Other company products specify a desirable haze value of 40% or less (for example, J Touch). Also, due to the required function of anti-glare effect, the established gloss value should not be too high (GU < 100). For all samples, the transmission value exceeds 90%. Moreover, the optical parameters of the sparkle, DOI / MTF (pixel pattern width and height of 244.5 μm each) and reflection Rs match well in comparison to commercial products.

Table 2.1 Summary of optical parameters

<Table 2.2> Summary of Optical Measurements (Continuation of Table 2.1)

*) Commercial products from Meihan Shinku Kogyo Co. Ltd. of Japan

**) Brand name

In Tables 2.1 and 2.2: Ra is the arithmetic mean of the absolute value of the profile deviation within the reference distance. Rz is the arithmetic mean of the largest individual illuminance from a plurality of adjacent individual measurement distances. Sparkle is defined as the ratio of the variance (σ) and the mean (μ) of the gray value distribution measured for the presented pixel pattern (defined by SMS 1000 instrument: sub-pixel width (57.4 μm) + gap width (187.1 μm ) = 244.5 [mu] m). The DOI / MTF is the ratio of the optical contrast of the object (here: image under the anti-glare film). The pixel pattern is defined as 244.5 μm by the SMS 1000 instrument. Rs is the percentage of the standard light reflection at a light incident angle of 45 [deg.].

Sample B-3-X was applied to a 1-M substrate while a B-4-X sample was applied to a 1-4 substrate.

For commercial antiglare films, the Rz value exceeds 600 nm. Gloss values below GU 85 are also preferred. Typically, a DOI / MTF value ≥ 95% is found.

A film having an Rz value > 600 nm is achieved for a 1-M substrate with a coating material thickness of <10 μm, in this case a gloss value GU <70 and a DOI / MTF value> 96%. For 1-4 films, an Rz value of > 600 nm is achieved for a coating material thickness of less than a value of 15 to 21 [mu] m. Here, the gloss value GU is < 70 and the corresponding DOI / MTF value is > 98%.

As apparent from Table 2, the coated film of the present invention has excellent anti-glare properties. Thus, the coated films according to the present invention were shown to have simultaneously scratch resistance and anti-glare properties combined with resistance to acetone, the most aggressive organic solvent for many other solvents, more particularly polycarbonate. Thus, the films of the present invention have excellent compatibility with industry applications in many fields, particularly those requiring a transparent, anti-glare surface with high mechanical and chemical durability. More particularly, the coated film of the present invention is suitable for use as a front pane of a computer screen, a television, a display system and a display of a cellular phone.

Claims (15)

(a) at least one thermoplastic polymer in an amount of at least 30% by weight of the solids content of the coating composition;
(b) at least one UV-curable reactive diluent in an amount of at least 30% by weight of the solids content of the coating composition;
(c) at least one photoinitiator in a solids content of the coating composition of &gt; = 0.1 to &lt; = 10 parts by weight; And
(d) at least one organic solvent
Wherein the solids content of the coating composition is in the range of &gt; 0 to &lt; = 40 wt%, based on the total weight of the coating composition
Coating composition. The coating composition of claim 1, wherein the ratio of ethylenically unsaturated groups is at least 3 mol per kg solids content of the coating composition. 3. The coating composition of claim 1 or 2, wherein the solvent (d) comprises 1-methoxy-2-propanol. 4. The coating composition according to any one of claims 1 to 3, wherein (a) the thermoplastic polymer has Vicat softening temperature VET according to ISO 306 of at least 90 占 폚. 5. A composition according to any one of claims 1 to 4, wherein the thermoplastic polymer comprises a copolymer of PMMA homopolymer and 70% by weight to 99.5% by weight methyl methacrylate and 0.5% by weight to 30% by weight methyl acrylate &Lt; / RTI &gt; An anti-glare, coated polymer film comprising an anti-glare surface and a polymer film having a coating on the surface, the coating being obtainable by coating using the coating composition according to any one of claims 1 to 5 Wherein the coating has a layer thickness in the range of &lt; RTI ID = 0.0 &gt; 2 &lt; / RTI &gt; 7. The coated polymeric film of claim 6, wherein the film comprises a polycarbonate film. The coated film according to claim 6 or 7, wherein at least one anti-glare surface of the uncoated polymer film is characterized by an illumination depth Rz according to DIN EN ISO 4287 in the range of? 800 and? 3600 nm. Polymer film. 9. A coated polymer film according to any one of claims 6 to 8, wherein the gloss value GU according to ASTM-D2457 at &lt; RTI ID = 0.0 &gt; 60 &lt; / RTI &gt; 10. A coated polymer film according to any one of claims 6 to 9, wherein the surface of the coating has an illuminance Rz according to DIN EN ISO 4287 of at least 600 nm. (i) providing a film having at least one anti-glare surface of the film;
(ii) film against the surface of the anti-glare surface
(a) at least one thermoplastic polymer in an amount of at least 30% by weight of the solids content of the coating composition;
(b) at least one UV-curable reactive diluent in an amount of at least 30% by weight of the solids content of the coating composition;
(c) at least one photoinitiator in a solids content of the coating composition of &gt; = 0.1 to &lt; = 10 parts by weight; And
(d) at least one organic solvent
Wherein the coating has a layer thickness in the range of ≥ 2 μm and ≤ 20 μm and the solids content of the coating composition is ≥ 0 to ≤ 40 wt% based on the total weight of the coating composition, A step within the range;
(iii) drying the coating;
(iv) optionally cutting the film to a specified size, delaminating, printing and / or thermally or mechanically molding the film; And
(v) irradiating the coating with actinic radiation to cure the coating
&Lt; / RTI &gt; At least one coated polymer film according to any one of claims 6 to 10, selected from the group consisting of an architectural glazing member, a covering plate glass and a front plate glass for displays, and a matte plastic part for electric, &Lt; / RTI &gt; 13. The product of claim 12, wherein the display is a computer screen, a television, a display system and a display of a mobile phone, wherein the matte plastic part is an electronic housing part or a built-in trim part of an automobile, a railway vehicle, a motor vehicle or an aircraft. Use of a coated polymer film according to any one of claims 6 to 10 as a high transparency anti-glare front pane for displays or as a matte plastic part for electric, electronic and automotive interior trim. 11. Use according to claim 10, wherein the display is a computer screen, a television, a display system and a display of a mobile phone, and the matted plastic part is an electronic housing part or a built-in trim part of an automobile, a railway vehicle, a motor vehicle or an aircraft.